Synthetic microporous solids containing gallium and phosphorous, their synthesis and their use as catalysts and adsorbents

Abstract

This invention relates to a crystalline synthetic microporous solid containing gallium and phosphorus, whose crystal structure is of the LTA type. After calcination at a temperature above 200° C. the solid obtained can be employed as a catalyst for converting hydrocarbons or as an adsorbent.

We claim: 
     
       1. A crystalline synthetic microporous solid containing gallium and phosphorous, having an LTA crystal structure, and in its anhydrous as-synthesized form, corresponds to the formula:   S.sub.s (Ga.sub.g P.sub.p X.sub.x Y.sub.y)O.sub.2 F.sub.f     wherein   S is an organic structuring agent;   X is a trivalent element;   Y is a tetravalent element; and   s,g,p,x,y and f denote the numbers of moles per two moles of oxygen atoms, and have a value:   
     
     
       0. 01≦s≦0.2 0.1≦g≦0.5   0.2≦p≦0.5   0≦x≦0.4   0≦y≦0.3   0.01≦f≦0.2    where g+p+x+y=1.   
     
     
       2. A solid of claim 1, wherein s is from 0.05 to 0.17. 
     
     
       3. A solid of claim 1, wherein g is from 0.35 to 0.5. 
     
     
       4. A solid of claim 1, wherein p is from 0.4 to 0.5. 
     
     
       5. A solid of claim 1 wherein x is from 0 to 0.1. 
     
     
       6. A solid of claim 1, wherein y is from 0 to 0.1. 
     
     
       7. A solid of claim 1, wherein f is from 0.12 to 0.17. 
     
     
       8. A solid of claim 1 wherein the trivalent element X is aluminium. 
     
     
       9. A solid of claim 1 wherein the tetravalent element Y comprises silicon. 
     
     
       10. A solid of claim 1 having an X-ray diffraction pattern which includes at least the values of d hkl  of Table I. 
     
     
       11. A solid of claim 1 wherein the organic structuring agent comprises at least one amine selected from the group consisting of primary and secondary amines. 
     
     
       12. A microporous solid obtained by calcining the solid of claim 1 at a temperature sufficient to remove at least a portion of the structuring agent. 
     
     
       13. A solid of claim 12, wherein the calcination temperature is above about 200°. 
     
     
       14. A solid according to claim 12 having an adsorption capacity of about 0.148 g of n-hexane per gram and a porosity of at least 0.22 cm 3  g -1 . 
     
     
       15. A process for the synthesis of a microporous crystalline solid of claim 1, which comprises: (a) forming a reaction mixture containing water, a source of gallium, a source of phosphorus, a source of fluoride anions and an organic structuring agent; (b) heating the mixture to a temperature of at least about 40° C. under at least autogenous pressure for a time sufficient to form a crystalline solid; and (c) recovering the crystalline solid. 
     
     
       16. A process of claim 15, wherein the reaction mixture contains a source of a trivalent element X. 
     
     
       17. A process of claim 15, wherein the reaction mixture contains a source of a tetravalent element Y. 
     
     
       18. A process of claim 15 wherein the molar composition of the reaction mixture comprises   s'S : Ga.sub.2 O.sub.3 : p'P.sub.2 O.sub.5 : x'X.sub.2 O.sub.3 : y'YO.sub.2 : f'F : hH.sub.2 O     where   s' is from 1 to 10;   p' is from 0.1 to 1;   x' is from 0 to 1;   y' is from 0 to 1.5;   f' is from 0.1 to 4; and   h is from 10 to 500.   
     
     
       19. A process of claim 15 wherein the source of fluoride anions comprises at least one composition selected from the group consisting of hydrofluoric acid, salts of hydrofluoric acid with alkali metals, salts of hydrofluoric acid with ammonium, salts of hydrofluoric acid with an organic structuring agent, ammonium fluorosilicate, sodium fluorosilicate and silicon tetrafluoride. 
     
     
       20. A process of claim 19 wherein the source of fluoride anions comprises hydrofluoric acid. 
     
     
       21. A process of claim 15 wherein the source of gallium is gallium oxide or gallium hydroxide. 
     
     
       22. A process of claim 15 wherein the source of gallium comprises an organic gallium composition. 
     
     
       23. A process of claim 15 wherein the source of gallium comprises at least one gallium salt selected from the group consisting of gallium fluoride, gallium phosphate and gallium sulphate. 
     
     
       24. A process of claim 15 wherein the source of phosphorus comprises at least one composition selected from the group consisting of phosphoric acid salts and phosphoric acid esters. 
     
     
       25. A process of claim 16 wherein the trivalent element comprises aluminium. 
     
     
       26. A process of claim 25 wherein the source of aluminium comprises at least one composition selected from the group consisting of aluminum oxide, aluminium hydroxide, aluminium alkoxide, boehmite, pseudoboehmite, gamma aluminum, aluminium salts and sodium aluminate. 
     
     
       27. A process of claim 17 wherein the tetravalent element comprises silicon. 
     
     
       28. A process of claim 27 wherein the source of silicon comprises a silicon oxide in the form of a hydrogel, an aerogel or a colloidal suspension. 
     
     
       29. A process according to claim 28 wherein the colloidal suspension is a colloidal suspension of silica. 
     
     
       30. A process of claim 29 wherein the silica is formed by hydrolysis of a silicate composition or precipitation from a silicate composition. 
     
     
       31. A process of claim 15 wherein the organic structuring agent is an amine. 
     
     
       32. A process of claim 31 wherein the amine is a dialkylamine. 
     
     
       33. A process of claim 32 wherein the alkyl groups each contain 2 to 4 carbon atoms. 
     
     
       34. A process of claim 15 wherein the pH of the reaction mixture is from 2 to 8. 
     
     
       35. A process of claim 34 wherein the pH of the reaction mixture is adjusted by the addition of at least one composition comprising at least one member selected from the group consisting of hydrochloric acid, sulphuric acid, acetic acid, ammonium hydrogen fluoride, sodium hydrogen sulphate, ammonia, sodium hydroxide, sodium hydrogen carbonate, sodium carbonate, methylamine, acetate buffer mixtures and ammoniacal buffer mixtures. 
     
     
       36. A process of claim 15 wherein the reaction mixture is heated to a temperature of from 40° to 250° C. for a period sufficient to produce crystallization. 
     
     
       37. A solid of claim 1 wherein p is from 0.4 to 0.5; x is from 0 to 0.1 and y is from 0 to 0.1. 
     
     
       38. A solid of claim 11 wherein the structuring agent comprises a secondary amine. 
     
     
       39. A solid of claim 13 wherein the calcination temperature is from about 200° C. to about 450° C. 
     
     
       40. A process of claim 18 wherein s' is from 5 to 10;   p' is from 0.5 to 1.0;   x' is from 0 to 0.5;   y' is from 0 to 1.0;   f' is from 1 to 3; and   h is from 30 to 100.   
     
     
       41. A process of claim 22 wherein the organic gallium composition comprises a gallium alkoxide. 
     
     
       42. A process of claim 23 wherein the source of gallium comprises gallium sulfate. 
     
     
       43. A process of claim 24 wherein the source of phosphorus comprises at least one member selected from the group consisting of alkali metal phosphate, gallium phosphate, and alkyl phosphate. 
     
     
       44. A process of claim 24 wherein the source of phosphorus comprises phosphoric acid. 
     
     
       45. A process of claim 26 wherein the source of aluminum comprises aluminium sulfate. 
     
     
       46. A process of claim 28 wherein the source of silicon comprises a colloidal suspension of silica. 
     
     
       47. A process of claim 33 wherein the alkyl groups each contain three carbon atoms. 
     
     
       48. A process of claim 34 wherein the pH is from about 3 to about 8. 
     
     
       49. A process of claim 36 wherein the reaction mixture is heated at a temperature of from 60° C. to 210° C.